Amphoteric surface-active organic compounds



Patented Oct. 6, 1959 AMPHOTERIC SURFACE-ACTIVE COMPOUNDS Adolf Schmitz and Gunther Cramer, Essen, Germany, assignors to The Goldschmidt A.G., Essen, Germany, a German company No Drawing. Application May 16, 1955 SerialNo. 508,768.

' Claimspriority, application May 28, Claims. 01. 260- 519) ORGANIC This invention relates to manufacture of amphoteric surface-active organic compounds; audit comprises a series of'organic compounds having the general; formula:

wherein x is an integer from 1 to 2, y ranges 0 to 3, but x plus y is not greater than 5, R represents a substituent' group selected from the class consisting of alkyl and aralkyl groups containing from 8 to 18 carbon atoms, A represents a divalent group selected from the class consisting of "-NR --(C H NH) and-NR -C H NH 2 being an integer from 1 to 3 and R representing a hydrogeiisuBstituent, and R represents a substituent selected from the class consisting of methyl, halogen, carboxyl and the group Thus such as bacteria, fungi or rickettsia, and these compounds have come into use as disinfectants. Among the cationactive compounds numerous quaternary ammoniumcompounds and quaternary phosphonium compounds have good bactericidal properties. In the amphoteric group of compounds derivatives of higher amino acids have achieved technical importance as disinfectants.

It has also long been known that certain phenols possess strong germicidal properties. Thus phenol itself, the cresoles and the higher homologues of phenol, hydroxydiphenyl and benzylphenol all possess such properties. 1

The germicidalelfects are increased when the benzene nucleus contains in addition to the hydroxyl group oertaiii" other substituents, such as halogen atoms. It is also known that aliphatic substituents, containing from 5 mo carbon atoms for gram-negativeand 8 to 9 carbon atoms 9 for gram-positive bacteria, increase the elfectiveness of thesephenol compounds.

The present invention involves the discovery of a new group of amphoteric compounds which possess unexpectedly high germicidal properties and which ionize in such fashion that the anion contains a phenolgrouping while the cation contains at least two basic nitrogen atoms, one of which is attached to at least one high molecular organic group. These new compounds have the following general formula:

wherein x is an integer from 1 to 2, y ranges from 0 to wherein A and R have their former significancies.

These compounds can be produced in accordance with the present invention by reacting at elevated temperatures an amine of the formula R AH with formaldehyde and with a phenol having the formula:

wherein R R A and y have their former significancies; the molecular proportions of amine and formaldehyde being about I 1:1 while the molecular proportions of amine to phenol are from about 1:1 to 2:1, depending upon the number of R ACH groups in the compound to be produced; and recovering the resulting amphoteric surface-active compound. The chemical reaction is usually exothermic butit is usually necessary to apply heat towards the end of the process in order to increase the'yields. Aqueous formaldehyde can be used in the process and, if desired, an inert organic solvent can be added to the reaction Zone.

The amines to be used in our process are primary amines having an alkyl or aralkyl group having from 8 to 18 carbonatoms and, in the case of secondary amines,

an alkyl group containing from 8 t0'18 carbon atoms,

and which may contain from two to four NH groups separated by ethylene or propylene groups. Specific examples are octyl amine, octyl-octadecyl amine, dodecylpropylene diamine, dodecyldiethylene triamine, octyldiethylene triamine, dodecylbenzyl triethylene tetramine, etc. The phenol to be employed may be phenol itself andphenols which are substituted with from 1 to 3 substituents, such as methyl groups, halogen groups, hydroxyl or carboxyl groups. Specific phenols found to be operative are phenol,'fo-, mand p-creso1, p-chloro-mcresol, p-chloro-m-Xylenol, p-hydroxy-benzoic acid, salicylic acid, etc. The formaldehyde can be employed in aqueous or alcoholic solution. p

' The novel compounds of the present invention are for themostpa'rt non-crystallizing hygroscopic oils, insoluble in water,' which give neutral or alkaline reactions, depending on the number of acid or alkaline groups therein.

On the addition of acids or alkalies to their aqueous suspensions, however, there result clear solutions of good foaming quality.

I The bacteriological eflicacy of our new compounds extends to gram-positive as well as gram-negative bacteria, this being an essential advantage over the cation-active surface-active compounds, and it exceeds that of the previously known amphoteric surface-active disinfectants 3 to 4 times. For instance, the compound of the following Example 8 reliably kills M icrococcus aureus, Escherichia coli and Bacterium proteus vulg. in a dilution of 1:8,000 after 10 minutes. Our compounds are also eflicacious against Microbacterium tuberculosis. Tubercle bacteria are killed by the compound of Example 9 in 0.1% solution after 30 minutes, in 0.05% solution after 60 minutes.

In the presence of serum the eflicacy is not appreciably impaired.

in practical use our'compounds are usually transformed into their salts with organic or mineral acids and then dissolved in water to give solutions containing from to 25% by weight of the salt. Some of the mineral acid salts are onlyslightly soluble in water and in these cases the salts of organic acids are used, for example the salts of formic, acetic and lactic acid can be employed. The salt solutions are usually diluted to a concentration of from about 0.05 to 2% before actual use which possess a considerably lower surface tension to water. A 0.1% solution of the acetate of the compound as per Example 10 has a surface tension of 32 dynes per centimeter. These solutions may have their pH values adjusted within the range of from about 4.5 to 8 without impairment of their effectiveness. This tolerance-t0 pH change represents an important advantage over the surface-active amino acid derivatives which are used as disinfectants. Our compounds are also effective throughout a relative wide temperature range, being effective from about to 75 C.

Solutions of our new compounds, because of their high bactericidal efficacy combined With their good detergent properties, are excellent for rough disinfection in hospitals, bathing establishments, wash rooms of industrial plants, toilets etc., as well as for disinfection of plants of the food industry, such as dairy operations, slaughterhouses, etc. In view of their high wetting and detergent effects these compounds represent an important advance in the field of germicidal and fungicidal agents having a cleaning action.

Our invention can be explained in greater detail by reference to the following specific examples which de scribe practical embodiments of our process of producing our novel amphoteric surface-active compounds.

Example 1.D0decyl-di-(aminoethyl)-amin0methylphenol A mixture is made of 94 parts by weight of phenol, 271 parts by weight of dodecyl-diethylenetriamine and 81 parts by weight of a 37% formaldehyde solution, corresponding to 30 parts by weight of formaldehyde. The reaction occursas in. Example 1 with intense evolution of heat and is completed by heating for one hour on a boiling water bath. The resulting light-yellow syrupy liquid'is soluble as a clear solution both in dilute bases and dilute organic acids, such as' acetic acid and lactic acid.

Dodecyl-aminoethyl-aminomethyl phenol can be obtainedby substituting 228 parts dodecyl-ethylenediamine for the 271 parts of dodecyl-diethylenetriamine used in the above process. Also dodecyl-aminopropyhaminomethyl phenol can be obtained by substituting 242 parts of dodecyl-propylene diamine'for the 271 parts of dodecyl-diethylenetriamine used in the above process.

Example 2.-Dodecyl-di-(aminoethyl)-amin0methyl-nchlora-m-cresol 271 parts by weight of dodecyl-diethylenetriamine are condensed with 142 parts by Weight of p-chloro-m-cresol and 30 parts by weightof formaldehyde as described in Example 1. After 1 /2 hours over the boiling water bath the reaction is terminated. The solubilities are the same as those described in Example 1.

215 parts byweight of octyl-diethylenetriamine and 108 parts by weightof p-cresol are reacted, as described above, with 30 parts of formaldehyde. After heating on a boiling water bath for one hour there is formed an oily yellow liquid which is soluble in both dilute alkalies and acids.

Example 4.-Octyl-di-(aminoethyl)-aminbmethyl pchloro-m-xylenol CH;- CH;

By reacting 215 parts by weight of octyl-diethylenetriamine, 156 parts byv weight of p-chloro-m-xylenol and 30 parts by weight of formaldehyde there results after 1 /2 hours at C. a yellow liquid having the same solubility properties as the compounds described above.

Example 5.-Manufact'ure o f dodecylbenz yl-triwminoethyl)-aminomethyl phenol solution of this compound in l minute.

6 used as a disinfecting-cleansingsolution, preferably after Exampie 6 .Bis- [octyl-di- (aminoethyl -amz'no methyl J dilution.

p cresol 21.9 parts by weight of octyldiethylenetriamine, 5.4

Example 8 .--Bis[dodecyl-di aminoethyl -aminme'thyl parts by Weight of p-cresol and 3 parts by weight of salicylic acid formaldehyde, as a 37% aqueous solution, are reacted together as above. The reaction product is a viscous yellowish liquid of distinctly amphoteric properties. On admixture of an aqueous suspension with concentrated 54.2 parts by weight of dodecyl-diethylenetriamine are 5 heated With 13.8 parts by weight of salicylic acid on a boiling'waterbath with mechanical agitation until a clear solution is obtained. The mixture is then cooled to 40 hydrochloric acid-the hexachloride is formed as a color- C. and then parts by Weight of a aqueous soluless, fine-crystalline P p having the ysis: tion of formaldehyde are added. This causes the tempera- 33 '72 6 6 781)-F0l1I1dI C1, 275%; 30 ture to rise to about 70 C. After the first reaction has N, 10.7%. Calculated: CI, 27.3%; N, 10.75 died down, heating is continued on a boiling waterbath Example 7.-Bis[d0decyl-di-(aminoethyl)-amin0meihyl]- or ot e o hours- A yellow-brown viscous i is p-chloro-m-cresol formed which is readily soluble in dilute acids and alkalies. From a 50% alcohol solution a fine-crystalline hexa 17.75 parts by Weight of p-chloro-m-cresol, 69.5 parts chloride canbe isolated after adding concentrated hydroby weight of dodecyldiethylenetriamine and 8 parts by Ci T a na y weight of formaldehyde as a 37% aqueous solution are f fifi gg9%% 9'23)' '-Found:

reacted. together as p d under.EXa.Igp1e 5 1 25 .16 parts by weight of the almostpure product are results in aviscous oil read ly soluble aci s an a ares dissolved with a mixtureyof 6556 cc of N/2 H01 and from Whlch a fille-clystallme hexachloflde 9am be Pbtamed 409 cc. of water with gentle heating. The concentration with concentrated hydrochloric acid. This 'hexachloride has the analysis:

of this solution is 5%. It is an excellent cleansing and disinfecting agent. C H ON CI (mol. wt. 92.7.5).--F0und: Ionogenic Example. 9.Bis- (dodecyl-diethylenetriaminomethyl) -p- 27 .8 parts by weight of dodecyldiethylejnetriamine are Ionogenic Cl, 23.0%; total C1, 26.80%; N, 9.06%. g fiig Z 3 g: ii z iygii ieilgg gg iizifdf i iii: Parts y weightvof the almost P reaction P scribed in Example 7, to form a yellow viscous paste. On net are ti d up i h 184 parts by eight f an treating a 50% alcohol solution of this with concentrated proximately 80% lactic acid Without addition of a solvent, hydrochloric acid While cooling w a fine-crystalline whereupon an intensive heat of neutralization develops. almost colorless hexachlonde 18 formed havmg the anal sis: After cooling, the still oily product is stirred into 740 cc. ciHasOaNsCls (mol. wt 923 1 227%;

of water to form a 10% clear solution. This can be N, 0.07%. Calculated: Cl, 23.1%; N, 9.1%,

Cl, 23.9%; total Cl, 26.86%; N, 9.75%. Calculated:

2,907,79 1 7 Example 1 0..- 2,2.-.b'is-. [p.-hydroxy:m,m'-di(dodecyldiethylenetriaminomethyl) -phenyl] -propane cal reaction of our processjattemperatures below; the boiling point of the reaction medium but higher tempera- I OH 22.8 parts by weight of 2,2-bis-(4,4-dioxy-diphenyl)- tures can be employed and superatmospheric pressures propane are mixed with 110.1 parts by weight of dodecylcan be s d if si other modifications Of Our diethylene-triamine and with 32.6 parts by weight of a p o ss Which l Within t scope of the following Claims 37% aqueous formaldehyde solution. After the initial will be immediately evident to those skilled in the art. reaction has died down, which reaction is accompanied W at We Cl im is by intensive evolution of heat, the product is heated on 1. Amphoteric surface-activeorganic compounds hava boiling waterbath for 1 hour. There is formed a very 5 ng the g r l r a viscous yellow oil which dissolves only slightly in water but readily in acids and alkalies. With concentrated hydrochloric acid there is formed a crystalline, slightly soluble salt which it was possible to identify as dodec'achloride. This has the analysis:

Cg H1q o N12Cl1 .-F0und: Cl, 23.3%, N, 9.2%. Calculated: Cl. 23.65%; N, 9.33%.

It is believed to be within the skill of the art, with the assistance of the above examples, to produce any of the specific compounds which fall within the scope of the general formula wherein x is an integer from 1 to 2, y ranges from 0 to 3, R represents a substituent group selected from the class consisting of "alkyl and aralkyl groups containing from 8 to 18 carbon atoms, A represents a divalent group selected from the class consisting of and --NR C H NH'-, z being an integer from 1 to 3 and R representing a hydrogen substituent, and R represents a substituent selected from the class consisting of methyl, halogen, carboxyl and the group since it is only necessary to react a phenol, substituted H with from 0 to 3 of the groups R y, with formaldehyde and with an amine of the formula R A-H at elevated temperatures, with the molar proportions of the amine and formaldehyde being 1:1 and the molar proportions of the amine and the phenol ranging from 1:1 to 3:1,

depending upon the number of R -ACH sub- 0H stituents desired in the compound and, of course, taking wherein A and R have their former significances.

into consideration the number ofpositions available for 2'. As a 7 new amphoteric surface-active compound substitution in the phenol nucleus. Thus x plus 1 can bis[dodecyl-di(aminoethyl)-aminomethyl] salicylic acid.

never equal more than 5. 3. As a new amphoteric surface-active compound do- While we have described what we consider to be the decyl-di-(aminoethyl)-aminomethyl-p-chloro-m-cresol.

most advantageous embodiments of our process and prod- 4. As a new amphoteric surface-active compound ocucts it is evident, of course, that various modifications tyl-di-(aminoethyl)-aminomethyl-p-cresol.

can be made in the specific procedures which have been 5. As a new amphoteric surface-active compound octyldescribed without departing from the purview of this indi-(arninoethyl)-aminomethyl-p-chloro-m-xylenol.

vention. Thus the several components of the chemical reaction which is involved in the production of our com- References Cited in the file of this Patent pounds can be dissolved or suspended in an inert organic UNITED STATES PATENTS solvent if desired but it is usually more convenient to em- 2,098,869 Harmon et al. Nov. 9, 1937 P 3 water s he t n Inedlum SII'ICG formaldehyde Bruson Oct 2 i re ily available in aqueous solution. Compounds 2,363,134 Mccleary 21, 1944 having different R A-CH substituents can be pro- 3 duced by'using a mixture of diflerent amines in place of a single amine. It is convenient to conduct the chemi- OTHER REFERENCES Bovet et al.: Chem. Abstracts 42, 982f 1948 

1. AMPHOTERIC SURFACE-ACTIVE ORGANIC COMPOUNDS HAVINGING THE GENERAL FORMULA 